JP2000503329A - N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigment suitable for aqueous coatings - Google Patents
N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigment suitable for aqueous coatingsInfo
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- JP2000503329A JP2000503329A JP9525650A JP52565097A JP2000503329A JP 2000503329 A JP2000503329 A JP 2000503329A JP 9525650 A JP9525650 A JP 9525650A JP 52565097 A JP52565097 A JP 52565097A JP 2000503329 A JP2000503329 A JP 2000503329A
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- dimethylperylene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
(57)【要約】 ペリレン−３，４−ジカルボン酸イミド−９−スルホン酸またはその塩およびＣ8〜Ｃ18−アルキルアミンまたはＣ8〜Ｃ18−アルケニルアミンの存在で、水性媒体中に懸濁されたジイミドを、カルボキシル基を含有する樹脂で被覆し、被覆されたジイミドを単離しかつ乾燥させ、引き続き乾式粉砕することによって得られる、水性塗料に適当なＮ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカルボン酸ジイミド顔料。 (57) Abstract: In the presence of perylene-3,4-dicarboxylic imide-9-sulfonic acid or a salt thereof and a C 8 -C 18 -alkylamine or a C 8 -C 18 -alkenylamine, the compound is suspended in an aqueous medium. The turbid diimide is coated with a resin containing carboxyl groups, the N, N'-dimethylperylene-3 suitable for aqueous coatings is obtained by isolating and drying the coated diimide and subsequent dry milling. , 4,9,10-tetracarboxylic diimide pigment.
Description
【発明の詳細な説明】 水性塗料に適当なＮ，Ｎ′−ジメチルペリレン−３， ４，９，１０−テトラカルボン酸ジイミド顔料 本発明は、ペリレン−３，４−ジカルボン酸イミド−９−スルホン酸またはそ の塩およびＣ8〜Ｃ18−アルキルアミンまたはＣ8〜Ｃ18−アルケニルアミンの存 在で、カルボキシル基を含有する樹脂で水性媒体中に懸濁されたジイミドを被覆 し、被覆されたジイミドを単離しかつ乾燥させ、引き続き乾式粉砕することによ って得られる、水性塗料に適当な新規Ｎ，Ｎ′−ジメチルペリレン−３，４，９ ，１０−テトラカルボン酸ジイミド顔料に関する。 更に、本発明は、この顔料の製造および水性塗料に顔料を添加するためのこの 顔料の使用ならびにこの顔料を含有する水性塗料に関する。 周知のように、Ｎ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカル ボン酸ジイミド（Ｃ．Ｉ．ピグメントレッド１７９）は、塗料系または他の高分 子有機系中に直接に混入する場合に顔料が添加された系の劣悪なレオロジー的性 質および満足できない色彩性をまねく形で合成の際に生じる。それゆえ、顔料の 付加的な処理によって、その使用上の性質を改善することが試みられている。 例えばドイツ連邦共和国特許出願公開（ＤＥ−Ａ）第２５０４４１８号明細書 には、透明で着色力の強いＣ．Ｉ．ピグメントレッド１７９の製造方法が記載さ れており、この場合には、ペリレン−３，４，９，１０−テトラカルボン酸二無 水物および水性メチルアミンからのジイミドの合成中に、加熱によって反応を完 了させるために樹脂酸が添加され、この樹脂酸は、顔料を単離する際に再び洗い 流されるかまたはアルカリ土類金属塩として顔料上に析出される。 ドイツ連邦共和国特許出願公開（ＤＥ−Ａ）第４３２５２４７号明細書から、 Ｃ．Ｉ．ピグメントレッド１７９のための顔料添加剤としてペリレン−３，４− ジカルボン酸イミド−９−スルホン酸またはペリレン−３，４−ジカルボン酸イ ミド−９−カルボン酸およびこれらの塩の使用は、公知であり、この場合にはま た、付加的に極性のアンカー基を有するポリマー、例えば２−（ジエチル）アミ ノエタノールのエチレンオキシド付加物およびプロピレンオキシド付加物を基礎 としたポリマーまたはポリエチレンイミンおよび６−カプロラクトンのブロック コポリマーが使用されることができる。添加剤および所望の場合にはポリマーを 有する顔料の被覆は、合成の際に水で湿ったプレスケーキとして単離されたジイ ミドおよび被覆剤の水性懸濁液を撹拌しかつ引き続き加熱することによって、ま たは水の存在または不在で被覆剤を有する予め乾燥し たジイミドを擦ることもしくは粉砕することによって行われる。このように被覆 されたＣ．Ｉ．ピグメントレッド１７９は、確かに被覆されていない顔料と比較 してレオロジーおよび色彩性（鮮やかな帯黄赤色で、透明に着色）に関連して明 白な改善を示すけれども、しかしながら特別に水性塗料中で使用されることがで きる顔料については全く記載されていない。 従って、本発明の課題は、好ましい使用特性を有する、水性塗料に適当なＮ， Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカルボン酸ジイミド顔料を 提供することを基礎としていた。 それに応じて、ペリレン−３，４−ジカルボン酸イミド−９−スルホン酸また はその塩およびＣ8〜Ｃ18−アルキルアミンまたはＣ8〜Ｃ18−アルケニルアミン の存在で、水性媒体中に懸濁されたジイミドをカルボキシル基を含有する樹脂で 被覆し、被覆されたジイミドを単離しかつ乾燥させ、引き続き乾式粉砕すること によって得られる、水性塗料に適当なＮ，Ｎ′−ジメチルペリレン−３，４，９ ，１０−テトラカルボン酸ジイミド顔料が見出された。 更に、Ｎ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカルボン酸ジ イミド顔料を製造するための本明細書中で定義された方法が見出された。 更に、水性塗料に顔料を添加するためのこの顔料の使用が見出された。 新規のＮ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカルボン酸ジ イミド顔料は、有利に本発明による方法に従って得られ、この場合には水性媒体 中でできるだけ微粒状に懸濁されているジイミドを、カルボキシル基を含有する 樹脂、ペリレン−３，４−ジカルボン酸イミド−９−スルホン酸もしくはその塩 およびＣ8〜Ｃ18−アルキルアミンもしくはＣ8〜Ｃ18−アルケニルアミンまたは これらの物質の反応生成物で被覆し、かつこうして被覆されたジイミドをその単 離後にさらに乾式粉砕する。 カルボキシル基を含有する樹脂として、特に天然樹脂および変性した天然樹脂 、殊にコロホニウム樹脂、例えばコロホニウム自体およびその一般に公知の誘導 体、例えば二量化コロホニウム、重合コロホニウム、水素添加コロホニウムおよ び不均化コロホニウムならびにマレイン酸またはフマル酸との反応生成物が適当 である。もちろん、これらの樹脂の混合物も使用されることができる。 一般に、ペリレン−３，４，９，１０−テトラカルボン酸二無水物に対して樹 脂２〜１５重量％、有利に８〜１２重量％が使用される。 顔料添加剤であるペリレン−３，４−ジカルボン酸イミド−９−スルホン酸は 、有利に遊離酸の形で使用されるが、しかしながら、アルカリ金属塩、例えばナ トリウム塩もしくはカリウム塩、アンモニウム塩また は（殊にＣ8〜Ｃ18−）アルキルアンモニウム塩として使用されることができる 。 ペリレン−３，４−ジカルボン酸イミド−９−スルホン酸の適当な量は、ペリ レン−３，４，９，１０−テトラカルボン酸二無水物に対して、一般に０．５〜 ４重量％、有利に１．５〜２重量％である。 アミンとしては、不飽和であってもよいがしかしながら好ましくは飽和されて いる、一般にＣ原子８〜１８個、有利にＣ原子１２〜１８個を有する脂肪族アミ ンが適当である。このようなアミンの中で、第一アミノ基を有する１価アミンが 特に適当である。例として、ｎ−オクチルアミン、ｎ−デシルアミン、ｎ−ドデ シルアミン、ｎ−テトラデシルアミン、ｎ−ヘキサデシルアミン（セチルアミン ）、オレイルアミンおよび殊にｎ−オクタデシルアミン（ステアリルアミン）が 挙げられる。 アミンは、通常は、ペリレン−３，４，９，１０−テトラカルボン酸二無水物 に対して、２〜１５重量％、有利に８〜１２重量％の量で使用される。 本発明によるジイミドの被覆は、水性媒体中にできるだけ微粒状に懸濁されて いる顔料粒子に対して行われる。このような懸濁液は、例えば、ジイミド合成の 際に生じる、水で湿ったプレスケーキを水中で撹拌することによるか、または単 離しかつ乾燥したジイミドを硫酸中に溶解させかつ引き続き水中で沈殿させるこ とによって得られることができる。 しかしながら、有利に、被覆は、ジイミド合成と組み合わされる、というのも 、こうして最も良好な結果が達成されかつ付加的に作業工程が節約されるからで ある。 Ｎ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカルボン酸ジイミド の合成は、有利に、ドイツ連邦共和国特許出願公開（ＤＥ−Ａ）第４３２５２４ ７号明細書に記載されているように、水中に懸濁されたペリレン−３，４，９， １０−テトラカルボン酸二無水物を、有利に40重量％の水溶液の形の２〜４倍の モル量のメチルアミンと反応させることによって行われる。この際、アミンの添 加は、約０〜１０℃、有利に０〜５℃に冷却しながら行われる。引き続き反応混 合物は、一般に５〜１０℃で２〜３時間および次に反応を完了させるために通常 は７０〜９０℃で１〜２時間撹拌される。 樹脂およびペリレン−３，４−ジカルボン酸イミド−９−スルホン酸は、メチ ルアミンを添加する前にペリレン−３，４，９，１０−テトラカルボン酸二無水 物の懸濁液に添加されるが、しかしながらこれらは、イミド化後に添加されても よい。アミン（殊にステアリルアミン）は、ジイミド形成後に添加される。有利 に、アミン溶液は、無水または含水の有機酸中、例えば氷酢酸もしくは希酢酸ま たは希無機酸、例えば硫酸 中で使用されるが、しかしながらアミンおよび酸は、互いに別々に添加されても よい。酸の存在によって、懸濁液のｐＨは低下され（通常のｐＨは約３〜５であ る）、かつメチルアンモニウム塩として溶解して存在する樹脂は顔料粒子上に析 出される。 処理技術的に好ましくは、イミド化の終結後に存在する反応混合物を約５０〜 ６５℃に冷却し、アミンおよび酸またはアミンの酸溶液を添加し、かつこの温度 で更に１〜３時間後撹拌するようにして行われる。 樹脂、ペリレン−３，４−ジカルボン酸イミド−９−スルホン酸およびアミン で被覆されたジイミドの引き続く単離は、室温への冷却後に常法で濾過し、水で 洗浄し、８０〜１００℃で乾燥することによって行うことができる。 本発明による方法の最終工程は、例えばボールミル中で有利に０．０２〜０． ０６μｍの平均粒径への被覆された乾燥ジイミドの粉砕であり、このことは一般 に３〜６時間継続される。 本発明による被覆されたジイミドは、簡単に粉砕されかつボールまたはミルの 壁に粘着しないように粉砕されることができ、かつ粉砕の際に極めて弛緩し、直 接に塗料製造に適した粉末として生じる。 本発明によるＮ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカルボ ン酸ジイミド顔料は、有利に水性塗料に顔料を添加するのに適当であり、かつこ の際、良好な湿潤性ひいては卓越した分散性および透明度ならびに鮮やかな帯黄 赤色の色調によって特徴付けられる。 例 Ａ）本発明によるＮ，Ｎ′−ジメチルペリレン−３，４，９，１０−テトラカル ボン酸ジイミド顔料の製造例１〜例６ ペリレン−３，４，９，１０−テトラカルボン酸二無水物１００ｇを水５００ ｍｌ中に搬入し、次に樹脂Ｋ ａ［ｇ］およびペリレン−３，４−ジカルボン酸 イミド−９−スルホン酸（塩）Ｐ ｂ［ｇ］を添加した。１時間の後撹拌後に、 懸濁液を氷３５０ｇの添加によって０℃に冷却し、４０重量％のメチルアミン水 溶液８０ｍｌの添加後に、最初に５℃で２時間、引き続き８０℃で１．５時間撹 拌した。６０℃に冷却した後に、氷酢酸１００ｍｌ中のアミンＡ ｃ［ｇ］の溶 液を添加した。 １時間の後撹拌および室温に冷却した後に、被覆されたジイミドを濾別し、水 で中性になるまで洗浄し、かつ８０℃で乾燥させた。 引き続き被覆された乾燥ジイミドそれぞれ３０ｇをメノウ球（直径５〜１５ｍ ｍ）２００ｍｌを有する５００ｍｌの粉砕用ビーカー中で高速遊星ミルで５時間 粉砕した。 この際、微粒状（平均粒径０．０２〜０．０６μｍ）で鮮やかな帯黄赤色で透 明でありかつ水性塗料中で極めて良好に分散可能なＮ，Ｎ′−ジメチルペリレン −３，４，９，１０−テトラカルボン酸ジイミド顔料それぞれ約２７ｇが得られ た。 更に、これらの試験ならびにその結果についての詳細は、次の表にまとめられ ている。例７ 例１と同様にして行ったが、しかしながらコロホニウム樹脂をイミド化後に初 めて、ステアリルアミン溶液の添加前に添加した。乾燥後に１２３ｇの被覆され たジイミドが生じた。 例８ ジイミドの合成を例１と同様に、しかしながらペリレン−３，４−ジカルボン 酸イミド−９−スルホン酸の存在だけで行った。４０℃に冷却後に、スルホン酸 で被覆されたジイミドを濾別し、かつ中性になるまで洗浄した。 次に湿ったプレスケーキを水５００ｍｌ中で撹拌した。引き続き２重量％の苛 性ソーダ液で懸濁液のｐＨを１０に調節し、次にコロホニウム樹脂を添加し、か つ１時間後撹拌した。その後、酢酸中のステアリルアミン溶液を添加した。１時 間の後撹拌後に、例１のようにして後処理した。被覆された乾燥ジイミド１１０ ｇが得られた。 比較例Ｖ１ 例１と同様にして行ったが、しかしながらペリレン−３，４−ジカルボン酸イ ミド−９−スルホン酸およびステアリルアミンで被覆されたジイミドの合成、単 離およびボールミル粉砕後に初めて、コロホニウム樹 脂（ジイミドに対して１０重量％）を混入した。 比較例Ｖ２ 例１と同様にして行ったが、しかしながらコロホニウム樹脂およびペリレン− ３，４−ジカルボン酸イミド−９−スルホン酸で被覆されたジイミドの合成、単 離およびボールミル粉砕後に初めて、ステアリルアミン（ジイミドに対して１０ 重量％）を混入した。 Ｂ）レオロジー特性および色彩性の評価 レオロジー特性を評価するために、着 色塗料を製造し、この場合固体含量２２重量％を有する市販の水を基剤とするポ リウレタン練り塗料８５ｇ中の顔料１５ｇずつを、スカンデクス(Skandex)装置 中で２時間、ＳＡＺ−ビーズ１００ｍｌを用いて分散させた。 着色塗料の評価は、その製造後３０分以内に次の尺度に基づいて行われた： １ 極めて良好に流動 ２ 良好に流動 ３ 中程度に流動 ４ 粘液状 ５ ペースト 例１〜例６ならびに例７および例８からの顔料は、評価点１または２と評価さ れたのに対し、比較のために製造された顔料は評価点４〜５が得られたのにすぎ なかった。 色彩性の評価のために、それぞれ全固体に対してペリルイミド顔料４重量％お よびアルミニウムフレーク４重量％を含有しかつ市販の水希釈性のバインダ系を 基礎としたメタリック塗料を製造した。得られたメタリック塗料を、白く下塗り された金属板に吹き付け、かつ焼き付けた。 例１〜例８からの顔料で得られた仕上げ塗り塗装は、比較顔料で得られた仕上 げ塗り塗装よりも黄色を帯びた赤色でありかつ明らかにより鮮やかであった。DETAILED DESCRIPTION OF THE INVENTION N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigment suitable for aqueous coatings The present invention relates to perylene-3,4-dicarboxylic imide-9-sulfone acid or a salt thereof and C 8 -C 18 - alkyl amine or C 8 -C 18 - in the presence of alkenyl amines, covering the suspended diimide in an aqueous medium with a resin containing carboxyl groups, the coated diimide A novel N, N'-dimethylperylene-3,4,9,10-tetracarboxylic acid diimide pigment suitable for aqueous coatings, obtained by isolating and drying and subsequently dry milling. Furthermore, the invention relates to the production of the pigment and to the use of the pigment for adding pigments to aqueous paints and to aqueous paints containing the pigment. As is well known, N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide (CI Pigment Red 179) is directly incorporated into paint systems or other high molecular organic systems. In this case, the poor rheological properties and unsatisfactory color properties of the pigmented systems occur during the synthesis. It has therefore been attempted to improve the use properties of the pigment by additional treatment. For example, German Offenlegungsschrift (DE-A) 2 504 418 discloses C.I. I. Pigment Red 179 is described, in which case the reaction is completed by heating during the synthesis of diimide from perylene-3,4,9,10-tetracarboxylic dianhydride and aqueous methylamine. To this end, a resin acid is added, which is washed off again during the isolation of the pigment or deposited on the pigment as an alkaline earth metal salt. From DE-A 43 25 247, C.I. I. The use of perylene-3,4-dicarboxylic imide-9-sulfonic acid or perylene-3,4-dicarboxylic imide-9-carboxylic acid and salts thereof as pigment additives for Pigment Red 179 is known. In this case also polymers having additionally polar anchor groups, for example polymers based on ethylene oxide and propylene oxide adducts of 2- (diethyl) aminoethanol or block copolymers of polyethyleneimine and 6-caprolactone Can be used. The coating of the pigment with the additives and, if desired, the polymer, is carried out by stirring and subsequently heating an aqueous suspension of the diimide and the coating agent, which was isolated as a wet cake with water during the synthesis. Or by rubbing or grinding a pre-dried diimide with a coating in the presence or absence of water. C. coated in this manner. I. Pigment Red 179 does show a distinct improvement in rheology and chromaticity (brilliant yellowish red, transparently colored) compared to uncoated pigments, however, especially in aqueous paints. No mention is made of pigments which can be used. The object of the present invention was therefore based on the provision of N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigments having favorable use properties and suitable for aqueous coatings. Accordingly, perylene-3,4-dicarboximide 9-sulfonic acid or a salt thereof and C 8 -C 18 - alkyl amine or C 8 -C 18 - in the presence of alkenyl amine, suspended in an aqueous medium N, N'-dimethylperylene-3,4, suitable for aqueous coatings, obtained by coating the diimide obtained with a resin containing carboxyl groups, isolating and drying the coated diimide, followed by dry milling. A 9,10-tetracarboxylic diimide pigment has been found. Furthermore, a process as defined herein for producing N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigment has been found. Furthermore, the use of this pigment for adding pigments to aqueous paints has been found. The novel N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigments are advantageously obtained according to the process according to the invention, in which case they are suspended as finely as possible in an aqueous medium. the in and diimide, a resin containing a carboxyl group, perylene-3,4-dicarboximide 9-sulfonic acid or a salt thereof and C 8 -C 18 - alkyl amine or C 8 -C 18 - alkenyl amines or their The diimide coated with the reaction product of the substance and thus coated is further dry-ground after its isolation. As resins containing carboxyl groups, in particular natural resins and modified natural resins, in particular colophonium resins such as colophonium itself and its generally known derivatives, such as dimerized colophonium, polymerized colophonium, hydrogenated colophonium and disproportionated colophonium and maleic Reaction products with acids or fumaric acid are suitable. Of course, mixtures of these resins can also be used. In general, from 2 to 15% by weight, preferably from 8 to 12% by weight, of resin are used, based on perylene-3,4,9,10-tetracarboxylic dianhydride. The pigment additive perylene-3,4-dicarboxylic imide-9-sulfonic acid is preferably used in the form of the free acid, however, alkali metal salts such as sodium or potassium salts, ammonium salts or ( in particular C 8 ~C 18 -) may be used as the alkyl ammonium salts. A suitable amount of perylene-3,4-dicarboxylic imide-9-sulfonic acid is generally 0.5 to 4% by weight, based on perylene-3,4,9,10-tetracarboxylic dianhydride. 1.5 to 2% by weight. Suitable amines are aliphatic amines which may be unsaturated but are preferably saturated and generally have 8 to 18 C atoms, preferably 12 to 18 C atoms. Among such amines, monovalent amines having a primary amino group are particularly suitable. Examples include n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine (cetylamine), oleylamine and especially n-octadecylamine (stearylamine). The amine is usually used in an amount of 2 to 15% by weight, preferably 8 to 12% by weight, based on perylene-3,4,9,10-tetracarboxylic dianhydride. The coating of the diimides according to the invention is carried out on pigment particles which are suspended as finely as possible in an aqueous medium. Such suspensions can be obtained, for example, by stirring a water-moist presscake which forms during the synthesis of the diimide in water, or by dissolving the isolated and dried diimide in sulfuric acid and subsequently precipitating in water. Can be obtained. Advantageously, however, the coating is combined with a diimide synthesis, since the best results are thus achieved and additional operating steps are saved. The synthesis of N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide is advantageously carried out as described in DE-A 43 25 247. Reacting perylene-3,4,9,10-tetracarboxylic dianhydride suspended in water with 2 to 4 times the molar amount of methylamine, preferably in the form of a 40% by weight aqueous solution Done by In this case, the addition of the amine is carried out while cooling to about 0 to 10 ° C, preferably 0 to 5 ° C. The reaction mixture is subsequently stirred, generally at 5-10 ° C for 2-3 hours and then usually at 70-90 ° C for 1-2 hours to complete the reaction. The resin and perylene-3,4-dicarboxylic imide-9-sulfonic acid are added to the suspension of perylene-3,4,9,10-tetracarboxylic dianhydride before adding methylamine. However, they may also be added after imidization. The amine, especially stearylamine, is added after diimide formation. Advantageously, the amine solution is used in an anhydrous or hydrous organic acid, such as glacial acetic acid or dilute acetic acid or a dilute inorganic acid, such as sulfuric acid, however, the amine and the acid may be added separately from one another. The presence of the acid lowers the pH of the suspension (usually the pH is about 3-5) and causes the resin, which is present as a solution as a methylammonium salt, to precipitate on the pigment particles. Technically preferred, the reaction mixture present after the end of the imidization is cooled to about 50-65 ° C., the amine and the acid or the acid solution of the amine are added and stirred at this temperature for a further 1 to 3 hours It is done as follows. Subsequent isolation of the resin, perylene-3,4-dicarboxylic imide-9-sulfonic acid and amine-coated diimide, was followed by conventional filtration after cooling to room temperature, washing with water, and 80-100 ° C. It can be performed by drying. The final step of the process according to the invention is preferably carried out, for example, in a ball mill at 0.02 to 0. Milling of the coated dry diimide to an average particle size of 06 μm, which is generally continued for 3-6 hours. The coated diimides according to the invention can be easily ground and ground so that they do not stick to the ball or the wall of the mill, and are very loose upon grinding, resulting directly in powders suitable for paint production . The N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigments according to the invention are preferably suitable for adding pigments to water-based paints, with good wettability and thus good wettability. It is characterized by excellent dispersibility and clarity and a vivid yellowish red hue. Example A) Preparation of N, N'-dimethylperylene-3,4,9,10-tetracarboxylic diimide pigment according to the invention Examples 1 to 6 Perylene-3,4,9,10-tetracarboxylic dianhydride 100 g were carried into 500 ml of water, and then resin Ka [g] and perylene-3,4-dicarboxylic imide-9-sulfonic acid (salt) Pb [g] were added. After stirring for 1 hour, the suspension is cooled to 0 ° C. by addition of 350 g of ice and, after addition of 80 ml of a 40% strength by weight aqueous methylamine solution, first for 2 hours at 5 ° C. and then for 1.5 hours at 80 ° C. Stirred. After cooling to 60 ° C., a solution of amine Ac [g] in 100 ml of glacial acetic acid was added. After stirring for 1 hour and cooling to room temperature, the coated diimide was filtered off, washed with water until neutral and dried at 80.degree. Subsequently, 30 g of each of the coated dry diimides were ground in a 500 ml grinding beaker having 200 ml of agate balls (5 to 15 mm in diameter) for 5 hours on a high-speed planetary mill. At this time, N, N'-dimethylperylene-3,4, which is fine-grained (average particle size 0.02 to 0.06 μm), is vivid yellowish red and transparent, and can be dispersed very well in an aqueous paint. About 27 g of 9,10-tetracarboxylic diimide pigment was obtained in each case. Further details of these tests and their results are summarized in the following table. Example 7 The procedure was as in Example 1, except that the colophonium resin was added only after the imidization and before the addition of the stearylamine solution. After drying, 123 g of the coated diimide resulted. Example 8 The synthesis of the diimide was carried out as in Example 1, but only in the presence of perylene-3,4-dicarboxylic imide-9-sulfonic acid. After cooling to 40 ° C., the sulfonic acid-coated diimide was filtered off and washed until neutral. The wet presscake was then stirred in 500 ml of water. Subsequently, the pH of the suspension was adjusted to 10 with 2% by weight of sodium hydroxide solution, then the colophonium resin was added and stirred after 1 hour. Thereafter, a solution of stearylamine in acetic acid was added. After stirring for one hour, the work-up was carried out as in Example 1. 110 g of the coated dry diimide were obtained. Comparative Example V1 The procedure was as in Example 1, but only after the synthesis, isolation and ball milling of the diimide coated with perylene-3,4-dicarboxylic imide-9-sulfonic acid and stearylamine, the colophonium resin ( 10% by weight based on diimide). Comparative Example V2 The procedure of Example 1 was repeated, except that the synthesis, isolation and ball milling of a diimide coated with a colophonium resin and perylene-3,4-dicarboxylic imide-9-sulfonic acid were carried out only after stearylamine ( 10% by weight based on diimide). B) Evaluation of rheological properties and color properties To evaluate the rheological properties, colored paints were prepared, in which case 15 g of pigment in 85 g of a commercially available water-based polyurethane mill paint having a solids content of 22% by weight were added. Was dispersed using 100 ml of SAZ-beads for 2 hours in a Skandex apparatus. The evaluation of the pigmented paint was carried out within 30 minutes after its production on the following scale: 1 very good flow 2 good flow 3 medium flow 4 viscous liquid 5 paste Examples 1 to 6 and 7 And the pigment from Example 8 was rated as 1 or 2, whereas the pigment produced for comparison only gave a score of 4-5. For the evaluation of the color properties, metallic paints were prepared, each containing 4% by weight of perilimide pigment and 4% by weight of aluminum flakes based on the total solids and based on a commercially available water-dilutable binder system. The resulting metallic paint was sprayed and baked onto a white primed metal plate. The finishes obtained with the pigments from Examples 1 to 8 were yellowish red and clearly more vivid than the finishes obtained with the comparative pigment.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 ペーター ブラシュカ ドイツ連邦共和国 ルートヴィッヒスハー フェン ダムシュテュッカー ヴェーク 127 (72)発明者 アルノー ベーム ドイツ連邦共和国 マンハイム シュタウ デンヴェーク 63────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Peter Brashka Germany Ludwigshahr Fen Damstucker Weg 127 (72) Inventor Arnaud Boehm Germany Mannheim Stau Denweg 63
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19601752A DE19601752A1 (en) | 1996-01-19 | 1996-01-19 | N, N'-Dimethylperylene-3,4,9,10-tetracarboxylic acid diimide pigment suitable for waterborne basecoats |
| DE19601752.1 | 1996-01-19 | ||
| PCT/EP1997/000064 WO1997026301A1 (en) | 1996-01-19 | 1997-01-09 | N,n'-dimethylperylene-3,4,9,10-tetracarboxylic acid diimide pigments suitable for water-based paints |
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| US (1) | US6099636A (en) |
| EP (1) | EP0880560B1 (en) |
| JP (1) | JP4073039B2 (en) |
| KR (1) | KR19990077121A (en) |
| CA (1) | CA2234111A1 (en) |
| DE (2) | DE19601752A1 (en) |
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| JP2007524749A (en) * | 2004-02-26 | 2007-08-30 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Perylene pigment composition and process thereof |
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| KR101148868B1 (en) * | 2004-01-26 | 2012-05-29 | 노오쓰웨스턴 유니버시티 | PERYLENE n-TYPE SEMICONDUCTORS AND RELATED DEVICES |
| US7569693B2 (en) * | 2006-06-12 | 2009-08-04 | Northwestern University | Naphthalene-based semiconductor materials and methods of preparing and use thereof |
| EP2089398A2 (en) * | 2006-10-25 | 2009-08-19 | Polyera Corporation | Organic semiconductor materials and methods of preparing and use thereof |
| WO2008063609A2 (en) * | 2006-11-17 | 2008-05-29 | Polyera Corporation | Diimide-based semiconductor materials and methods of preparing and using the same |
| CN101622253B (en) * | 2007-01-08 | 2015-04-29 | 破立纪元有限公司 | Methods for preparing arene-bis(dicarboximide)-based semiconducting materials and related intermediates for preparing same |
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| CH485008A (en) * | 1967-11-03 | 1970-01-31 | Geigy Ag J R | Process for the production of strong, transparent perylene pigments |
| FR1576477A (en) * | 1968-04-24 | 1969-08-01 | ||
| GB1313147A (en) * | 1970-08-08 | 1973-04-11 | Ciba Geigy Uk Ltd | Pigment compositions |
| DE2316536C3 (en) * | 1973-04-03 | 1981-08-20 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of strongly colored and easily distributable perylene-3,4,9,10-tetracarboxylic acid diimides |
| CH588530A5 (en) * | 1975-02-04 | 1977-06-15 | Hoechst Ag | |
| DE2727484C2 (en) * | 1977-06-18 | 1985-10-17 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of a red pigment from perylene-3,4,9,10-tetracarboxylic acid-N, N'-bis-methylimide |
| DE2837731A1 (en) * | 1978-08-30 | 1980-03-13 | Basf Ag | METHOD FOR THE PRODUCTION OF PIGMENT FORMS OF PERYLENE-3,4,9,10-TETRACARBONIC ACID DIIMID WITH HIGH GLAZE AND BRILLIANCE |
| JPS55164252A (en) * | 1979-05-18 | 1980-12-20 | Toyo Ink Mfg Co Ltd | Preparation of azo pigment |
| DE3018006A1 (en) * | 1980-05-10 | 1981-11-12 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING PIGMENTS OF THE PERYLENE-3,4,9,10-TETRACARBONIC ACID RANGE AND THE USE THEREOF |
| DE3101885A1 (en) * | 1981-01-22 | 1982-08-26 | Basf Ag, 6700 Ludwigshafen | PERYLENE-3,4,9,10-TETRACARBONSAEUREDIIMID DYE |
| DE3208192A1 (en) * | 1982-03-06 | 1983-09-08 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING PERYLENE-3,4,9,10-TETRACARBONIC ACID-N, N'-DIALKYL-DIIMID PIGMENTS |
| DE3436206A1 (en) * | 1984-10-03 | 1986-04-03 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING MIXED-CRYSTAL PIGMENTS BASED ON PERYLENTETRACARBONIC ACID DIIMIDES AND THE USE THEREOF |
| DE3524535A1 (en) * | 1985-07-10 | 1987-01-22 | Hoechst Ag | METHOD FOR PRODUCING PERYLENE-3,4,9,10-TETRACARBONIC ACID-N, N'-DIMETHYLIMIDE IN HIGH-COVERING PIGMENT FORM |
| DE4325247A1 (en) * | 1993-07-28 | 1995-02-02 | Basf Ag | Pigment preparations with perylene derivatives as dispersants |
-
1996
- 1996-01-19 DE DE19601752A patent/DE19601752A1/en not_active Withdrawn
-
1997
- 1997-01-09 WO PCT/EP1997/000064 patent/WO1997026301A1/en not_active Application Discontinuation
- 1997-01-09 KR KR1019980705257A patent/KR19990077121A/en not_active Application Discontinuation
- 1997-01-09 JP JP52565097A patent/JP4073039B2/en not_active Expired - Fee Related
- 1997-01-09 US US09/101,444 patent/US6099636A/en not_active Expired - Fee Related
- 1997-01-09 EP EP97900580A patent/EP0880560B1/en not_active Expired - Lifetime
- 1997-01-09 CA CA002234111A patent/CA2234111A1/en not_active Abandoned
- 1997-01-09 DE DE59703671T patent/DE59703671D1/en not_active Expired - Fee Related
-
1998
- 1998-05-14 MX MX9803845A patent/MX9803845A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007524749A (en) * | 2004-02-26 | 2007-08-30 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Perylene pigment composition and process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4073039B2 (en) | 2008-04-09 |
| EP0880560A1 (en) | 1998-12-02 |
| EP0880560B1 (en) | 2001-05-30 |
| US6099636A (en) | 2000-08-08 |
| WO1997026301A1 (en) | 1997-07-24 |
| DE59703671D1 (en) | 2001-07-05 |
| CA2234111A1 (en) | 1997-07-24 |
| MX9803845A (en) | 1998-09-30 |
| DE19601752A1 (en) | 1997-07-24 |
| KR19990077121A (en) | 1999-10-25 |
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